Carbohydrate derived polymers



United States Patent Ice No Drawing. Original application Sept. 20,1962, Ser. Nod

225,168, now Patent No. 3,225,012, dated Dec. 21, 1965. Divided and thisapplication June 16, 1965, Ser. No. 527,997

4 Claims. (Cl. 26088.3)

This application is a division of application Ser. No. 225,168 filedSept. 20, 1962, now US. Patent No. 3,225,- 012 which was acontinuation-in-part of now abandoned application Ser. No. 140, 618,filed Sept. 25, 1961.

This invention relates to several classes of polymeric materials havingexceptional commercial promise. More particularly, our invention relatesin one major aspect to optically active polymethacrylate polymerscontaining substituted or unsubstituted hexitol residues and moreparticularly such residues of D-glucose, D-glucitol, D- mannitol,L-iditol, galactitol and the corresponding mono and dicarboxylic acids,residues, which polymethacrylate polymers are easily converted into anovel type of watersoluble methacrylate containing a hydrocarbonbackbone having potential free aldehyde-containing glucose residuesattached to every other carbon atom. This water-soluble polymethacrylategives rise to derivatives of commercial promise by chemical treatment,for example by reduction, oxidation, acetylation, methylation,carbanilation, and phenylhydrazone and diphenylformazan formation. Ournovel polymethacry-late may have advantages over natural glucosepolymers, such as starch and cellulose, in being more reactive and lessreadily attacked by microorganisms.

The second major aspect of our invention relates to optically active,high-viscosity polyvinyl ethers containing the above describedsubstituted hexitol residues, which polyvinyl ethers can be convertedinto water-soluble polymers that contain a hydrocarbon backbone havingpotential free aldehyde-containing glucose residues attached to everyother carbon atom. Such water-soluble polyvinyl ethers would be expectedto have all the desirable properties of the above-mentionedpolymethacrylate, and in addition should be even more stable because theglucose residues are attached to the hydrocarbon backbone by etherlinkages in the polyvinyl ether in contrast to ester linkages in thepolymethacrylate.

The third major aspect of our invention relates to the practicalpreparation of nylon-type polyamides containing the aforesaidcarbohydrate residues, which carbohydratecontaining polyamide polymersare not subject to the prior art handicaps of substantial darkening ofthe product during polymerization and do not develop the excessivebrittleness that prevents the cold drawing of fibers thereof.

Although the general polymerization of glucose and other carbohydrateswith acidic catalysts has been extensively studied, only a few specificcarbohydrate monomers containing functional groups capable ofpolymerization in a given direction to give polymers of particularinterest have been prepared. One method of polymerizing substitutedcarbohydrates is by introducing a vinyl-type group into the monomer,which may then be capable of polymerizing to give a long hydrocarbonchain with sugar residues attached to alternate carbon atoms. Reppe etal., US. 2,157,347 polymerized 2,3:4,5 di Oisopropylidene-l-O-vinyl-D-fructose to a low molecular Weight resinousproduct soluble in organic solvents. Mikhantev et al., Zhur. Obshsh.Khim., 27, 2840 (1957) prepared 1,2:5,6 di O isopropylidene 3 O vinyl aD- glucofuranose by a high-temperature reaction between di- 3,404,136Patented Oct. 1, 1968 isopropylideneglucose and acetylene, but they didnot attempt to polymerize this monomer. Whistler et al., Jour. Org.Chem, 26, 1583 (1961) prepared 1 acrylamid-oand 1 methacrylamido l deoxyD glucitol and polymerized the monomers to give vinyl-type polymerscontaining hydrophilic sugar residues. Haworth et al., Jour. Chem. Soc.,488 (1946), polymerized 1,4:3,6 dianhydro 2,5 di O methacryloyl Dmannitol and 1,4:3,6 dianhydro 2,5 di O methacryloyl D- glucitol atWithout a catalyst to infusible, insoluble resins. They also found thatthe 1,6 di O acryloyl and methacryloyl esters of 2,4:3,5 di O methylene-D mannitol and di O methylene D glucitol behaved similarly. Wolfrom etal., Jour. Amer. Chem. Soc., 81, 5701 (1959) prepared 3 O acryloyl Dmannitol pentanitrate which polymerized with benzoyl peroxide to form alow-molecular-weight, gummy polymer. The 3- O methacryloyl esterpolymerized spontaneously to a hard solid.

Haworth et al., Jour. Chem. Soc., (1944) at tempted to prepare polyamidefibers by condensing 1,6- diamino 1,6 dideoxy 2,4:3,5 di O methylene D-mannitol at 210 to 250 C. with a dibasic acid such as oxalic, adipic,sebacic, and di O methylene L idaric acid, but the condensation productswere darkly colored, and the fibers drawn from the melt were brittle andcould not be cold drawn. Hamamura et al., J our. Agr. Chem. Soc., Japan,18, 1092 (1942) unsuccessfully tried to prepare polyamides with 1,6diaminodimethylenemannitol. Wiggins, Jour. Chem. Soc., 384 (1946)reacted l,2:5,6- dianhydro 3,4 O isopropylidene D mannitol at 150 to C.with 1,6 diaminodimethylenemannitol, but the resin which formed was oflittle interest because of its insolubility. Wolfrom et al., Jour. Amer.Chem. Soc., 80, 6328 (1958), prepared hydroxy polyamides by condensingtetra O acetylgalactaroyl dichloride with ethylenediamine or piperazinebut the acetylated polyamides were insoluble in common organic solventsand decomposed above 250 without melting. Butler et al., British Patent750,822 have formed linear polyamides by condensing a diamine at hightemperature with di O- methylene-, di O ethylideneand di Oisopropylidene-galactaric acid.

A principal object of our invention is the preparation of the 3 Omethacryloyl ester of 1,2:5,6 di O isopropylidene a D glucofuranose andrelated sugars for polymerization. Another object is the preparation ofpure 3 O vinyl ether of 1,2:5,6 di O isopropylidene a D glucofuranosefor polymerization to a highviscosity polyvinyl ether. Another object isthe preparation of nylon-type polyamides. Another object is thepreparation of 1,6 diamino 1,6 dideoxy 2,4:3,5 di O-methylene-D-glucitol dihydrochloride, 1,6-diamino-1,6- dideoxy 2,4:3,5di O methylene L iditol and its dihydrochloride, 1,6 diamino di Obenzylidene 1,6- dideoxygalactitol, and 1,6 diamino 1,6 dideoxy di- 0isopropylidenegalactitol, which novel compounds are essentialintermediates in the formation of high-viscosity, nylon-type polyamides.Another object is the preparation of 2,4:3,5 di O methylene D glucaroyldichloride and 2,4:3,5 di O methylene L idaroyl dichloride, thesecompounds also being essential intermediates in the formation ofhigh-viscosity nylon-type polyamides. Still another object is animproved method of forming the above nylon-type polyamides that avoidsany injurious or destructive thermal effects on the formed polyamide.The above and related objects will become fully apparent from a readingof the examples and appended claims.

In the instant invention we have prepared synthetic linearhigh-viscosity carbohydrate polyamides by the interfacialpolycondensation of a substituted diamino-dideoxysugar alcohol derivedfrom hexose sugar alcohols such as D mannitol, D glucitol (sorbitol), Liditol, or galactitol (dulcitol) and a dibasic acid chloride, e.g.,sebacoyl, adipoyl or terephthaloyl chloride, or by a similarpolycondensation of a substituted sugar dicarboxylic acid chloride, suchas a hexaroyl dichloride derived from a sugar acid such as D glucaric.(saccharic) acid, L- idaric acid, or galactaric (mucic) acid, witheither any ordinary diamine such as hexamethylenediamine ordecamethylenediamine, or with One of the above substituted diaminodideoxy sugar alcohols.

Representative of the substituted diamino dideoxy sugar alcohols whichare operative in preparing the improved and useful nylon-type polyamidesof our invention are:

1,6-diamino-1,6-dideoxy-diO-rnethylene-D-mannitol,1,6-diamino-1,6-dideoxy-di-O-methylene-D-glucitol,1,6-diamino-1,6-dideoxy-di-O-methylene-Ldditol,1,6-diamino-1,6-dideoxy-di-O-methylenegalactitol,1,6-diamino-di-O-benzylidene-1,6-dideoxygalactitol, 1,6-diamino1,6-dideoxy-di-O-isopropylidenegalactitol.

Similarly, representative carbohydrate'derived diacid chlorides include:

Di-O-methylene-D-glucaroyl dichloride, Di-O-methylene-L-idaroyldichloride, Di-O-methylenegalactaroyl dichloride,Tetra-O-acetylgalactaroyl dichloride.

The selected diamine or its dihydrochloride is dissolved in watercontaining the required amount of alkali and reacted with the diacidchloride in a water-immiscible solvent as taught by Magat et al., US.2,708,617 and 2,831,834.

Where the hydroxyl-protecting groups in the substituted diamino-dideoxysugar alcohol are methylene residues, as in1,6-diamino-1,6-dideoxy-di-O-methylene-D-mannitol,1,6-diamino-1,6-dideoxy-di-O-methylene-D-glucitol,l,6-diamino-1,6-dideoxy-di-O-methylene-L-iditol, and1,6-diamino-1,6-dideoxy-di-O-mcthylenegalactitol,

these methylene residues cannot be removed after the polycondensationwithout decomposing the polymer, but where the protecting groups areisopropylidene residues, as in 1,6diamino-1,6-dideoxy-di-O-isopropylidenegalactitol whose preparation is aprincipal object of this invention, these can be removed afterpoly/condensation by mild acid treatment to give a linear, insoluble,infusible tetrahydroxy-nylon, which has exceptional commercial promise.

The diamines synthesized from D-mannitol, D-glucitol, and L-iditol, andthe substituted D-glucaroyl and L- idaroyl dichlorides, all give rise tooptically active polyamides which may have special utility aslight-filter components.

EXAMPLE 1 1,2 5 ,6-di-O-isopropylidene-3 -O-meth acryloyl-a-D-glycofuranose Diisopropylideneglucose g.) in dry pyridine (100 ml.) washeated at 65 C. for 3.5 hours with methacrylic anhydride (20 ml.); water(50 ml.) was then added, and the mixture was heated for a further hourwith stirring. After standing overnight at C., the reaction mixture wasextracted with three 100 ml. portions of petroleum ether (B.P. 30-40)and the petroleum extracts were washed with three 100 ml. portions of 5percent sodium hydroxide solution, and then with water. The extractswere dried over sodium sulphate, tetrachlorohydroquinone (20 mg.) added,the solution concentrated, and the resulting syrup was distilled twiceto give a pure monomeric product as a colorless, viscous syrup whichslowly crystallized, M.P. 34-35 C. The yield varied from to percent indifferent preparations. B.P. 120 C./0.20 mm.

Hg; n 1,4614; [111 9 -370 in ethanol, -40.0 in chloroform, and 32.2 intetrachloroethane (c. 1).

Analysis.-C H O requires C, 58.51; H, 7.37; CH =C(CH )CO, 21.03%. Found:C, 57.7; H, 7.22; CH -(CH )CO, 19.7.

The monomer showed no OH absorption at 3400 cm.- in the infrared.

EXAMPLE 2Poly(1,2:5,6-di-O-isopropylidene-3-O-rnethacryloyl-u-D-glucofuranose)The pure monomer of Example 1 (40.84 g.) was polymerized in benzene (41ml.) in a nitrogen atmosphere by heating at 70 C. for 25 hours in thepresence of azobisisobutyronitrile (408 mg.). Further benzene (41 ml.)was then added and the acetonated polymer was precipitated by pouringthe viscous solution into 2 liters of methanol with stirring. The solidwas centrifuged, redissolved in boiling benzene ml.), and reprecipitatedwith 2 liters of methanol to give 31.21 g. (76.4% yield) of a Whitepolymer with the following characteristics: M.P. 214-218 C.; [a] 47.6 intetrachloroethane (c., 0.5).

Analysis.-C H O requires C, 58.51; H, 7.37%. Found: C, 58.32, H, 7.35.

The inherent viscosity, :c.- ln (m /1 of a solution of the polymertetrachloroethane was 0.50 dl./g. (c., 0.5 g./ ml.; 25 C.). The polymerwas soluble in chlorinated hydrocarbons and benzene but insoluble inalcohol and water.

EXAMPLE 3 Poly(3-O-methacryloyl-D-glucopyranose) 20 g. of the polymer ofExample 2 was hydrolyzed for 2 hours in 400 ml. of l N HCl at 100 withrapid stirring, the acetone being allowed to escaped from the reactionflask. Insoluble material was removed at the centrifuge, washed withwater, and the solution and washings neutralized with 4 N sodiumhydroxide solution. The solution was dialyzed against tap-waterovernight to remove chloride, filtered through kieselguhr, the filtrateconcentrated to 100 ml., and poured into 670 ml. ethanol. The polymerwas separated by centrifugation, washed with ethanol and ether, anddried over P 0 to a White powder (11.21 g.). Yield, 74.1%. [m] +49.8 inwater (0., 0.5). The inherent viscosity was 0.42 in water.

Analysis.C H O requires C, 48.38; H, 6.50%. Found: C, 48.1; H, 6.39.

The polymer was strongly reducing as the result of carbon atom 1 of theglucose residue being free.

EXAMPLE 4 Poly(3-O-methacryloyl-D-glucitol) 79.7 mg. of the polymer ofExample 3 was reduced with sodium borohydride (25.6 mg.) in 8 ml. water,the reac tion being allowed to proceed for 23 hours at 20 C. The finalspecific rotation of the solution was +3.5. The solution was madeslightly acid with 2 N acetic acid, concentrated to 5 ml., and pouredinto 28 ml. ethanol. The reduced polymer was separated bycentrifugation, washed with ethanol and ether, and dried over P 0 to awhite powder (61.4 mg.). Yield, 76.5%.

EXAMPLE 5 Poly(3-O-methacryloyl-D-gluconic acid) 508.5 mg. of thepolymer of Example 3 was dissolved in 4 M acetic acid (25 ml.), M sodiumchlorite (20 ml.) added, the solution made up to 50 ml., and thereaction allowed to proceed for 26 hr. at 20. The solution was dialyzedagainst running water overnight to remove excess chlorite and aceticacid, concentrated to small volume, passed through an Amberlite resinIR-H column to remove cations from the polyacid, and the eluate andwashings freeze-dried to give the polyacid as a white solid (491 mg).Yield, 90.7%. The product contained 83.2% of the theoretical carboxylcontent.

This polyacid was readily converted into its sodium salt. The abovewhite solid (98.7 mg.) was dissolved in 0.01 N sodium hydroxide (50ml.), the excess alkali neutralized exactly with 0.01 N sulphuric acid,and the solution dialyzed against distilled water to remove sodiumsulphate. The filtered dialyzate was freeze-dried to give the sodiumsalt as a white solid (78 mg). Yield, 73%. [d] +3 in water (c., 0.45).The inherent viscosity was 0.47 in water.

Analysis.C H O Na) requires Na, 8.0%. Found: Na, 8.0.

The properties of this salt resembled those of sodium alginate. Forexample, its solution in water was notably viscous and it gave insolubleprecipitates with various polyvalent cations, including calcium, barium,cupric, lead, ferrous, nickel, cobalt, ferric and aluminum.

EXAMPLE 6 Poly( 1,2 4,6-tetra-O-acetyl-3 O-rnethacryloyl-D-glucopyranose) To 997 mg. of the polymer of Example 3 dissolved in 50ml. dimethylformamide were added acetic anhydride (12 ml.) and pyridine(6 ml.), and the solution kept at C. for 24 hours and then poured intowater. The product which separated was purified by solution inchloroform (15 ml.) and reprecipitation with 150 ml. petroleum ether(B.P. 40-60"). The tetra-acetate was centrifuged and dried to a whitepowder (1.32 g.). Yield, 79.0%. [u] +43.4 in tetrachloroethane (c.,0.5). The inherent viscosity was 0.38 in tetrachloroethane.

Analysis.(C H O requires C, 51.93; H, 5.81; OHgCO, 41.36%. Found: C,51.3; H, 6.20; CH CO, 41.2.

EXAMPLE 7 Methylation of poly(3-O-methacryloyl-D-glucopyranose) To 97.9mg. of the polymer of Example 3 dissolved in dimethylformamide (4 ml.),[methyl iodide (1.5 ml.) and dry silver oxide (1.5 'g.) were added inportions, and the mixture shaken at 20 C. overnight. Residue wascentrifuged, washed with dimethylformamide (5 ml.) and chloroform (5ml.); the centrifugate and washings were treated with 1 percentpotassium cyanide solution (50 ml.), and the mixture extracted withchloroform (5 x 10 ml.). The combined extracts were washed with water,dried over sodium sulphate, concentrated to 10 ml., and poured into 100ml. petroleum ether (B.P. 40-60"). The precipitate was centrifuged,washed with petroleum ether, and dried to a white powder (95.9 mg). 81.8mg. of this partially methylated polymer was further methylated withmethyl iodide (5 ml.) and silver oxide (1 g.) at 45 C. for 6 hours. Thesilver residue was filtered, washed with boiling chloroform (3 X 5 ml.)and the filtrate and washings concentrated to 10 ml. and poured into 100ml. petroleum ether (B.P. 40-60). The product was methylated again inthe same way and finally isolated as a white powder (63.7 mg.). [a]+14.9 in tetrachloroethane (c., 1).

Analysis.The fully methylated polymer, (C H O requires OCH 40.80%.Found: OCH 36.0.

\EXAMPLE 8 Poly(3-O-methacryloyl-tri-O-phenylcarbamoyl-D- glucopyranose)202 mg. of the polymer of Example 3 was dissolved in dimethylformamide(10 ml.). Phenylisocyanate (1 ml.) was added, and the solution washeated at 100 C. for 3 hours. The solution was then poured into 100 ml.ethanol to precipitate the product, which was washed with ethanol andether and dried. The product was treated again in the same way, andpurified by solution in acetone (10 ml.) and reprecipitation in 100 ml.petroleum ether (B.P. 40- 60). The precipitate was finally washed withpetroleum 6 ether and dried to a white powder (379 mg.), which analyzedwell for the polymer tri(phenylcarbamate). Yield, 76.8%. [a] -|25.5 intetrachloroethane (c., 0.5 The inherent viscosity was 0.32 intetrachloroethane. Analysis.--(C H N O requires C, 61.46; H, 5.16; N,6.94%. Found: C, 60.9; H, 5.10; N, 6.91.

EXAMPLE 9 Poly(3-O-methacryloyl-D-glucosephenylhydrazone) 97 mg. of thepolymer of Example 3 was dissolved in 10 percent acetic acid (10 ml.)and 1 ml. of freshly distilled phenylhydrazine was added. Theyellow-orange colored Poly(3-O-methacryloyl-D-glucose diphenylformazan)A solution of phenyldiazonium chloride was prepared in accordance withMester et al., J our. Amer. Chem. Soc., 77, 4297 (1955), by dissolving2.5 g. of freshly distilled aniline in 18 percent (w./w.) HCl (12.5ml.), cooling the solution to O to 5 C., adding 2 g. of sodium nitritein 4 ml. water dropwise with stirring, and diluting the solution to 25ml. 1 m1. of this solution was then added dropwise with stirring to 95.7mg. of the polymer phenylhydrazone of Example 9 in pyridine-ethanol (1:1by volume; 10 ml.) which was cooled below 5 C. After 10 minutes thebright red precipitate was poured into ice-water (60 ml.), and after 20hours the polymer diphenylformazan was centrifuged, washed with water,and dried to a red powder (122.8 mg). Yield, 98.1%.

EXAMPLE l1 1,2:5,6-Di-O-isopropylidene-3-O-vinyl-a-D- glucofuranoseDiisopropylideneglucose (25 g.), isobutyl vinyl ether (250 ml.), andmercuric acetate (6.25 g.) were refluxed for 6 hr., and the solutionrapidly cooled, washed with three 100 ml. portions of 5% sodiumhydroxide solution to remove unreacted diisopropylideneglucose, anddried over sodium sulphate. The solution was concentrated to 20 ml.Petroleum ether (B.P. 60-80"; 100 ml.) was added, and furtherdiisopropylideneglucose was allowed to crystallize out. The filtrate wasthen treated with ultrasonically dispersed sodium (5 g.) in petroleumether ml.) under nitrogen for 45 min. to decompose organo-mercurycompounds, and the sodium amalgam centrifuged, washed with petroleumether, and the centrifugate and washings left overnight. A furtherprecipitate was separated, the solution concentrated, and the syrupdistilled to give the monomeric product as a colorless oil (4.156 g.).Yield, 15.1%. B.P. 84/ 0.05 mm. Hg; m, 1.459; [ab-26 in ethanol (c.,0.5).

Analysis.Calc. for C H O C, 58.7; H, 7.75%. Found: C, 58.6; H, 7.5.

Infrared analysis showed the characteristic vinyl doublet at 1645 and1620 cmf there was no OH absorption in the infrared. Most of theunreacted diisopropyli-deneglucose could be recovered from the 5% sodiumhydroxide was liquors by extraction With chloroform to give yields ofmonomer varying from 50 to 75% in different preparations.

EXAMPLE 12 Poly( 1,2 5 ,6-di-O-isopropylidene-3 -O-vinyl-a-D-glucofuranose) The monomer of Example 11 was redistilled three timesfrom sodium wire just before polymerization. The pure monomer (4.98 g.)was dissolved in methylene chloride (5 ml.) and hexane (15 ml.), thesolution cooled to '--78 C., and 12 drops of boron trifluoride etheratecatalyst added gradually over 80 min. Thirty minutes after the firstsign of polymerization, the reaction was stopped by the addition ofconcentrated ammonia solution (5 ml.) and methanol (50 ml.). The crudepolymer was purified by dissolving in chloroform (50 ml.) and pyridine(1 ml.) and slowly adding the filtered solution to stirred methanol (500ml.) The fibrous polymer was washed with methanol and dried to a whitepowder (3. 85 g.). Yield, 77.4%. [a] +2 in tetrachloroethane (c., 0.5);M.P. 210-212.

Analysis.--(C H O requires C, 58.7; H, 7.75%. Found: C, 58.7; H, 7.9.

The inherent viscosity was 0.65 in tetrachloroethane. The polymer wassoluble in chloroform and tetrachloroethane, and insoluble in benzene,ether, dioxan, acetone, ethyl acetate, and water. A carbohydrate vinylether has not hitherto been polymerized to a high-molecular-weightlinear polymer.

EXAMPLE 13 Poly 1 ,6-dideoxy-di-O-methylene-l-seb acamido-D- mannitol) Asolution of sebacoyl dichloride (721 mg.; 3.02 mmol.) in 50 ml. CCl wasadded at 20 C. to a rapidly stirred solution of1,6-diamino-l,6-dideoxy-di-O-methylene-D-mannitol dihydrochloride (836mg.; 3.02 mmol.) in 0.4 N sodium hydroxide (30.2 ml.; 12.08 mmol.). Theresulting polyamide was sequentially washed with 0.1 N HCl, 0.1 N sodiumhydroxide, water, alcohol and ether, and dried in vacuo over P to awhite, fibrous product (584 mg). Yield, 52.2%. [a] +85 in m-cresol (c.,0.5). The inherent viscosity, m =c." 1n (n j 1 of a solution of thepolymer in m-cresol was 0.80 dL/g. (c., 0.5 g./100 ml.; lIt melted at165175 C. Without decomposition and was soluble in dimethylformarnide,dimethylsulphoxide, m-cresol, and formic acid.

Analysis.(C I-I N O requires N, 7.56%. Found: N, 7.40.

EXAMPLE 14 Poly( 1,6-dideoxy-di-O-methylenel-terephthalamidd D-mannitol)A solution of pure terephthaloyl dichloride (3 mmol.) in ml. CCL, 'wasadded at 0 to a rapidly stirred solution of1,6-diamino-1,6-dideoxy-di-O-methylene-D-mannitol dihydrochloride (3mmol.) in 0.4 N sodium (30 ml.; 12 mmol.). The polyterephthalamide wasisolated in 78.7% yield as in Example 13 [OL:|D+83 in m-cresol (c.,0.5). It melted at 110230 C. without decomposition and had similarsolubility characteristics to the polymer of Example 13. Its inherentviscosity was 0.65 in m-cresol.

Analysis.-(C H N O requires C, 57.5; H, 5.4; N, 8.4%. Found: C, 55.9; H,5.7; N, 8.1.

EXAMPLE 15 1,6-diamine-1,6-dideoxy-di-O-methylene-D-glucitoldihydrochloride 1,6 dichloro 1,6 dideoxy 2,4:3,5 di Omethylene-D-glucitol (6.7 g.), prepared according to the teachings ofHaworth et al., Jour. Chem. Soc., 58 (1944), was heated with 31% (w./v.)aqueous ammonia solution (120 ml.) at 110115 C. for 24 hr. The solutionwas evaporated to dryness, the solid dissolved in water 1111.), and thesolution passed through a column of Amberlite resin IRA-401-OH to removechloride. The eluate was conoentrated, and the crude diamine (5.07 g.)was dissolved in water (10 ml.). Concentrated hydrochloric acid (5.7ml.) was added at 0, and crystallization was effected by adding ethanol(20 ml.). The product was recrystallized three times from aqueousethanol to give 1,6-diamino-l,6- dideoxy 2.4:3.5 O methylene D glucitoldihydrochloride (2.17 g.). Yield, 28.4%, [a] +36.8 in water (c., 1).

Analysis.-C H N O -2HCl requires C, 34.7; H, 6.54; C1, 25.6; N, 10.1%.Found: C, 34.2; H, 6.45; CI, 25.0; N, 9.9.

8 EXAMPLE 16 Poly( 1 ,6-dideoxy-di-O-rnethy1enel-sebacamido- D-glucitol)A solution of sebacoyl dichloride (3 mmol.) in 50 ml. CCL, was added at0 to a rapidly stirred solution of the diamine dihydrochloride (3 mmol.)of Example 15 in 0.4 N sodium hydroxide (30 ml.; 12 mmol.). Thepolyamide was isolated in 55.9% yield as in Example 13. [a] '3i2 inrn-cresol (c., 0.5). It decomposed above 270 without melting. It wasinsoluble in dimethylformamide, dimethylsulphoxide, and formic acid, andsoluble in m-cresol. Its inherent viscosity was 1.20 in m-cresol.

11rzalysis.-(C H N O requires C, 58.4; H, 8.2; N, 7.6%. Found: C, 57.7;H, 8.2; N, 7.0.

EXAMPLE l7 1,6-diamino-1,6-dideoxy-dhO-methylene-L-iditol2,4:3,5-di-O-methylene-L-iditol (2 g.), prepared according to Hann etal., Jour. Amer. Chem. Soc., 67, 602 (1945) was sustended in drypyridine (17 ml.). Thionyl chloride (10 ml.) was added, and the mixturerefluxed at for 30 min. The product was worked up according to themethod of Haworth et al., J our. Chem. Soc., 58 (1944) for thecorresponding glucitol derivative. The yellow solid (1 g.) wasrecrystallized from ethanol (200 ml.), and the crystals extracted withcarbon disulfide to remove contaminating sulphur and give pure1,6-dichloro-1,6-dideoxy- 2,4:3,5-di-O-methylene-L-iditol (533 mg.) in22.5% yield. M.P. 236.5-237"; [Ot]n+64.4 in chloroform (c., 1.4).

Analysis.C H Cl O requires C, 39.5; H, 4.98; Cl, 29.2%. Found: C, 39.1;H, 5.17; Cl, 29.3%.

The 1,6 dichloro-1,6-dideoxy-2,4:3,5-di-O-methylene- L-iditol (2.2 g.)was treated with 31% (w./v.) aqueous ammonia (40 ml.) at -115 C. for 24hr. as described in Example 15 for the glucitol derivative, and thecrude diazine (1.28 g.) sublimed at C./0.050.l mm. Hg to give pure1.6-diamino-1,6-dideoxy-2,4:3,5-di-O-methylene-L-iditol (685 mg.) in37.1% yield. M.P. 210-212 (decomp); [0C]D+19 in m-cresol (c., 0.5).

Analysis.C H N O requires C, 47.1; H, 7.88; N, 13.7%. Found: C, 47.2; H,7.94; N, 13.5.

EXAMPLE 18 1,6-diamine-1,6-dideoxy-di-O-rnethylene-L-iditoldihydrochloride The diamine (1.213 g.) of Example 17 in water (2.5 ml.)was treated at 0 with concentrated hydrochloric acid (1.4 ml.) andethanol (10 ml.) to give crystalline 1.6-diamino-1,6-dideoxy-2,4-:3,5-di- O- methylene-L-iditol dihydrochloride (832 mg.) in 50.5% yield.[Ot]n+13 in water (c., 0.5).

Analysis.C H N O -2HCl requires C, 34.7; H, 6.54; Cl, 25.6; N, 10.1%.Found: C, 34.3; H, 6.60; Cl, 25.2; N, 9.8.

EXAMPLE 19 Poly( 1,6-dideoxy-di-O-methylene-l-sebacamido-L-iditol) Asolution of sebacoyl dichloride (3 mmol.) in 50 m1. CCL, was added at 0to a rapidly stirred solution of the diaminedihydrochloride (3 mmol.) ofExample 18 in 0.4 N sodium hydroxide (30 ml.; 12 mmol.). The polyamidewas isolated in 80.8% yield as in Example 13. [0L]D-69 in m-cresol (c.,0.5). It decomposed above 320 C. without melting. It was sparinglysoluble in formic acid and m-cresol, and insoluble in dimethylformamideand dimethylsulphoxide. Its inherent viscosity was 0.91 in m-cresol.

Analysis.-(C H N o requires C, 58.4; H, 8.2; N, 7.6. Found: C, 57.3; H,8.2; N, 7.3.

EXAMPLE 20 Poly( 1,6-dideoxy-di-O methylene-l-sebacamidogalactitol) (1)A solution of sebacoyl dichloride (770 mg; 3.22 mmol.) in 54 ml. CCL,was added at C. to a rapidly stirred solution of1,6-diamino-1,6-dideoxy-di-O-methylenegalactitol (658 mg; 3.22 mmol.) in0.2 N sodium hydroxide (32.2 ml.; 6.44 mmol.). The polyamide wasisolated in 68.9% yield as in Example 13. The polymer was opticallyinactive. It melted at 200-206 C. without decomposition and had similarsolubility characteristics to the polymer of Example 13. Its inherentviscosity was 0.84 in m-cresol.

Analysis.--(C H N O requires C, 58.27; H, 8.16; N, 7.56%. Found: C,57.9; H, 8.22; N, 7.75.

(2) A solution of sebacoyl dichloride (760 mg.; 3.18 mmol.) in 50 ml.CCl was added at 20 C. to a rapidly stirred solution of1,6-diamino-1,6-dideoxy-di-O-methylenegalactitol dihydrochloride (880mg.; 3.18 mmol.) in 0.4 N NaOH (31.8 ml.; 12.72 mmol.). A polyamidehaving similar properties to that of Example 20(1) was obtained but witha higher inherent viscosity (0.95 in m.- cresol).

Analyszs.(C H N o requires N, 7.56%. Found: N, 7.34.

EXAMPLE 21 Poly( 1-adipamido-1,6-dideoxy-di-o methylenegalactitol) Asolution of adipoyl dichloride (256 mg; 1.40 mmol.) in 25 ml. CCL; wasadded at 5 C. to a rapidly stirred solution of1,6-diamino-1,6-dideoxy-di-O-methylenegalactitol dihydrochloride (388mg.; 1.40 mmol.) in 0.4 N NaOH (14 ml.; 5.6 mmol.). The polyamide (220mg.) was isolated in 49.9 percent yield with an inherent viscosity of0.36 in m-cresol. M.P. 226-235 C.

Analysis.(C H N O requires N, 8.92%. Found: N, 8.27.

EXAMPLE 22 Poly( 1,6-dideoxy-di-O-methylenel-terephthalamidogalactitol Asolution of pure terephthaloyl dichloride (3 mmol.) in 50 m1. CC], wasadded at 0 to a rapidly stirring solution of1,6-diamino-1,6-dideoxy-di-O-rnethylenegalactitol dihydrochloride (3mmol.) in 0.4 N sodium hydroxide (30 ml.; 12 mmol.) to give thepolyamide in 91.9% yield. It melted at 265-275 without decomposition. Itwas sparingly soluble in dimethylsulphoxide, formic acid, and m-cresol.Its inherent viscosity was 0.61 in m-cresol.

Analysis.(C H N O requires C, 57.5; H, 5.4; N, 8.4%. Found: C, 56.5; H,5.6; N, 8.0.

EXAMPLE 23 1,6-diamino-di-O-benzylidene-1,6-dideoxygalactitol Dryhydrogen chloride gas was passed through an agitated suspension of1,6-dichloro-1,6-dideoxygalactitol (6.056 g.), prepared according to theteachings of Butler et al., Jour. Chem. Soc., 636 (1956), inbenzaldehyde (42 ml.) for 4 hr. The solid was was filtered, washed withpetroleum ether and water, and recrystallized twice from ethanol (800:ml.) to give pure di-O-benzylid-ene-1,6-dichloro-1,6-dideoxygalactitol(5.952 g.) in 54.5% yield. M.P. 1534.

Analysis.C H Cl O requires C, 60.8; H, 5.10; Cl, 17.9%. Found: C, 61.2;H, 5.31; Cl, 18.2.

This dibenzylidenedichlorogalactitol (1.11 g.) was heated at 145-l50 C.for 72 hr. with dry methanol saturated with ammonia at 0 C. (80 ml.).The solution was concentrated, the solid dissolved in methanol (60 ml.)and water (30 ml.), and chloride removed with Amberlite resinIRA-401-OH. The eluate and washings were concentrated, and the crudediamine was distilled (bath temp. 250-280" C./0.01 mm. Hg) to givecrystalline 1,6-diamino diO-benzylidene-1,6-dideoxygalactitol in 39.5%yield.

10 Analysis.C H N O requires N, 7.86%. Found: N, 7.89.

EXAMPLE 24 Poly(di-O-benzylidene-1,6-dideoxy-1- sebacamidogalactitol) Asolution of the diamine (1.5 mmol.) of Example 23 was dissolve-d inethanol (30 ml.), and the solution titrated to pH 6 with 0.1 Nhydrochloric acid (30 ml.) to give a solution containing 1.5 mmol. ofthe diamine dihydrochloride. The solution was concentrated in vacuo at40 to 20 ml. to remove ethanol, cooled to 0, a sold solution of sebacoyldichloride (1.5 mmol.) in CCl, (50 ml.) was added and followedimmediately by the addition of 0.5 N sodium hydroxide (12 ml.; 6 mmol.)and the solutions mixed for 10 min. The polyamide was isolated in 74.5%yield. It melted at 210-220 C. It was soluble in dimethylfor-mamide,dimethylsulphoxide, formic acid, and m-cresol. Its inherent viscositywas 0.41 in m-cresol.

Analysis.(C H N O requires N, 5.36%. Found: N, 5.23.

EXAMPLE 25 1,6-diamino-1,6-dideoxy-di-O-isopropylidenegalactitol1,6-dichloro-1,6-dideoxygalactitol (1.008 g.), prepared according to themethod of Butler et al., Jour. Chem. Soc., 636 (1956) was shaken at 20for 19 hours with dry acetone (12.5 ml.) containing 0.1 ml. sulphuricacid. Further acetone (10 ml.) was added, the solution neutralized withanhydrous Na CO and the filtrate concentrated. The resulting crystallineresidue (1.323 g.) was twice recrystallized from 20 ml. petroleum ether(B.P. 60-80) to give1,6-dichloro-1,6-dideoxy-di-O-isopropylidenegalactitol (862 mg.) in 62.7percent yield. M.P. 114.5-115 C. Infrared analysis showed the absence ofOH absorption.

Analysis.-C H Cl O requires C, 48.16; H, 6.74; CI, 23.69%. Found: C,47.7; H, 6.80; Cl, 23.77.

This 1,6-dichlorodiisopropylidenegalactitol (5 g.) was heated with 31percent (w./v.) aqueous ammonia solution (160 ml.) at 115 for 4 /2 dayswith occasional shaking. The solution was concentrated to dryness, theresidue dissolved in 100 ml. water, and the solution passed through acolumn 175 ml.) of Amberlite resin IRA401- OH to remove chloride. Theeluate was concentrated in the absence of carbon dioxide and the productdistilled to give crystalline1,G-diamino-1,6-dideoxy-di-O-isoproplyidenegalactitol (2.536 g.) in58.3% yield, B.P. 9698 C./0.05 mm. Hg; M.P. 6971 C.

Analysis.C H N O requires C, 55.37; H, 9.29; N, 10.76%. Found: C, 54.8;H, 9.05; N, 11.02.

EXAMPLE 26 Poly 1 ,6-dideoxy-di-O-isopropylidene-1 sebacamidogalactitolA solution of sebacoyl dichloride (3.467 g.; 14.5 mmol.) in 230 ml. CCl,at 0 was added to a cold solution of the1,6-diamino-1,6-dideoxy-di-O-isopropylidene galactitol (3.775 g.; 14.5mmol.) of Example 25 in 0.2 N sodium hydroxide (145 ml.; 29 mmol.), andthe solutions were mixed in a macerator for 5 min. The polymer waswashed with 0.01 N hydrochloric acid, 0.1 N sodium hydroxide and water.The crude product was extracted with boiling ethanol ml.), and theextract poured into dilute sodium chloride solution (21.). Theprecipitate was washed with water to give the polyamide as a white,fibrous product (3.903 g.). Yield, 63.1%. It melted at -135. It wassoluble in ethanol, chloroform, dimethylformamide, zdimethylsulphoxide,formic acid, and m-cresol. Its inherent viscosity was 0.94 in m-cresol.

Analysis.-(C H N O requires C, 61.9; H, 9.0; N, 6.6%. Found: C, 61.3; H,8.9; N, 6.35.

The molten polyamide yielded filaments.

1 1 EXAMPLE 27 Poly(1,6-dideoxy-l-sebacamidogalactitol), i.e.,tetrahydroxy-nylon The acetonated polyamide (508 mg.) of Example 26 wasdeacetonated by heating at 100 C. in a sealed tube for 2 hours with 0.1N methanolic HCl (30 ml.) containing water (1.5 ml.). Thetetrahydroxy-nylon which precipitated was washed with water and dried toa powder (329 mg; 79.7% yield). This hydroxy-polyamide was infusible andinsoluble in the usual polyamide solvents with the exception of formicacid. The inherent viscosity was 0.36 in formic acid.

EXAMPLE 28 Di-O-methylene-D-glucaroyl dichloride Finely powdered,anhydrous di-O-methylene-D-glucaric acid (5 g.), prepared according tothe method of Haworth et al., Jour. Chem. Soc., 61 (1944), was refluxedfor 6 hr. with thionyl chloride (25 ml.), excess thionyl chlorideremoved in vacuo, the crude acid chloride refluxed With dry carbontetrachloride (300 ml), and the insoluble material filtered. Onconcentration the filtrate gave crystals, which were washed with lightpetroleum ether to give 2,4:3,5-di-O-methylene-D-glucaroyl dichloride(4.90 g.). Yield, 84.6%. M.P. 70; [a] +73.5 in benzene, +66.5 inm-cresol (c., 1).

Analysis.--C H Cl O requires C, 35.4; H, 2.97; Cl, 26.15%. Found: C,35.7; H, 3.08; Cl, 26.1.

EXAMPLE 29 Poly (hexarnethylene-di-O-methylene-D-glucaramide) A solutionof the diacid chloride (3 mmol.) of Example 28 in 75 ml. CCL, was addedat to a rapidly stirred solution of hexamethylenediamine (3 mmol.) in0.2 N NaOH (30 ml.; 6 mmol.). The crude product was purified bydissolving in 25 ml. dimethylformamide and pouring the filtered solutioninto saturated NaCl solution (100 ml.). The precipitate was washedthoroughly with water to give a tough, rubbery polyamide in 68.2% yield.[lX +56 in m-cresol (c., 0.5). It decomposed above 270 without melting.It was soluble in chloroform, dimethylformamide, dimethylsulphoxide,formic acid and m-cresol. Its inherent viscosity was 1.08 in m-cresol.

AnalysiS.-(C H N O requires C, 53.5 H, 7.1; N, 8.9%. Found: C, 51.6; H,7.2; N, 8.4.

EXAMPLE 3O Di-O-methylene-L-idaroyl dichloride Finely powdered, puredi-O-methylene-L-idaric acid (5.01 g.), prepared in accordance withHaworth et al., Jour. Chem. Soc, 61 (1944), was refluxed with purethionyl chloride (100 ml.) for hr., the mixture cooled, dimethoxyethane(100 ml.) added with cooling, and refluxing continued until the aciddissolved. The hot solution was filtered, and the filtrate cooled to 0to give crystalline 2,4:3,5-di-O-methylene-L-idaroyl dichloride (4.49g.). Yield 77.5%. M.P. 217220 C.; [OL]D+135 in benzene (0., 0.2), +143in m-cresol (c., 0.5).

Analysis.C H Cl O requires C, 35.4; H, 2.97; CI, 26.15%. Found: C, 35.5;H, 3.31; Cl, 26.0.

EXAMPLE 31 Poly (hexamethylene-di-O-methylene-L-idaramide) A solution ofthe diacid chloride (4.352 g.; 16.05 mmol.) of Example 30 in 400 ml.methylene chloride Was added at 20 C. to a solution ofhexamethylenediamine (1.865 g.; 16.05 mmol.) in 0.2 N NaOH (160 ml.; 32mmol.) and the solutions mixed in a high-speed macerator. The polyamide(2.821 g.; 55.9% yield) was obtained as a white fluify, fibrous materialwith a very high specific rotation ([OL]D19 +284 in m-cresol; c., 0.5).The

12 polymer did not melt below 320 C. Its inherent viscosity was 0.95 inm-cresol.

AnalysiS.(C H N O requires C, 53.5; H, 7.1; N, 8.9%. Found: C, 52.8; H,7.2; N, 8.7.

EXAMPLE 32 Poly(decamethylene-di-O-m'ethyleneL-idaramide) A solution ofthe diacid chloride of Example 30 in methylene chloride was added to asolution of decamethylenediamine in 0.2 N NaOH as described in Example31 to give a polyamide in 48.6% yield having an inherent viscosity of0.73 in m-cresol. [011 +238 in m-cresol (c., 0.5). The polyamidedecomposed above 320 C. without melting.

Analysfls.(C H N- O requires C, 58.4; H, 8.2; N, 7.6%. Found: C, 57.7;H, 8.2; N, 7.3.

EXAMPLE 33 Poly (hexamethylene-di-O-methylenegalactaramide) A solutionof di-O-methylenegalactaroyl dichloride (19 g.; 70.1 mmol.) in 1170 ml.CCl was added to a solution of hexamethylenediarnine (8.143 g.; 70.1mmol.) in 0.5 N NaOH (280 ml.; mmol.) and the solutions mixed in ahigh-speed macerator. The polyamide (17.05 g.; 77.4% yield) was obtainedas a white product, which melted at 200210 C. to a viscous liquid. Itsinherent viscosity was 0.97 in m-cresol.

Analysis.-(C H N O requires C, 53.5; H, 7.1; N, 8.9%. Found: C, 53.3; H,7.2; N, 8.75.

EXAMPLE 34 Poly (hexamethylene tetra-O-acetylgalactar amide) A solutionof tetra-O-acetylgalactaroyl dichloride (631 mg.; 1.52 mmol.) in 25 ml.CCl was added at 20 C. to a rapidly stirred solution ofhexamethylenediamine (176 mg.; 1.52 mmol.) in 0.2 N NaOH (15.2 ml.; 3.04mmol.). The polyamide (279 mg; 39.9% yield) was obtained as a white,free-flowing powder with an inherent viscosity in m-cresol of 0.34. Thepolymer, which is tetraacetoxynylon, was optically inactive.

AnalysiS.(C H N O requires C, H, N, 6.1%. Found: C, 52.3; H, 6.77; N,6.2.

EXAMPLE 3 5 Poly 1 ,6-dideoxy-di-O-mehylene- 1-(di-O-methylenegalactaramido) galactitol] A solution ofdi-O-methylenegalactaroyl dichloride (3 mmol.) in 50 ml. CCL, was addedat 0 to a rapidly stirred solution of 1,6diamino-1,6-dideoxy-di-O-methylenegalactitol dihydrochloride (3 mmol.)in 0.4 N NaOH (30 ml.; 12 mmol.). The polyamide was obtained as a whitepowder in 24.1% yield having an inherent viscosity of 0.39 in m-cresol.The polymer was optically inactive.

Analysis.(C H N O requires C, 47.8; H, 5.5; N, 7.0%. Found: C, 47.4; H,5.7; N, 6.6.

We claim:

1. 1,2:5,6-di-O-isopropylidene 3 O-vinyl-a-D-glucofuranose.

2. Poly(1,2:5,6 di O-isopropylidene-3-O-vinyl-a-D- glucofuran-ose) 3. Aprocess of preparing 1,2:5,6-di-O-isopropylidene3-O-vinyl-a-D-glucofuranose of high purity comprising refluxingdiisopropylideneglucose with isobutyl vinyl ether and mercuric acetatefor 6 hrs., successively washing with 5% NaOH solution, drying thewashed solution over sodium sulfate, concentrating the thusly driedsolution, adding petroleum ether to crystallize residual unreacteddiisopropylideneglucose, filtering, treating the filtrate under nitrogenwith highly dispersed sodium in petroleum ether, centrifuging,concentrating the centrifugate to a syrup, and distilling the syrup toyield the desired product as a colorless oil.

4. A process of preparing a high-molecular weight, linear homopolymer of1,2:5,6-di-O-isopropylidene-3-O- vinyl-a-D-glucofuranose comprisingcooling the monom'er solution to 78 C., slowly adding boron trifluorideetherate in dropwise manner, adding concentrated ammonia solution andmethanol to stop the polymerization reaction, isolating the crudepolymer, dissolving the crude polymer in a 50:1 mixture of chloroformand pyridine,

No references cited.

JOSEPH L. SCHOFER, Primary Examiner.

HARRY WONG, JR., Assistant Examiner.

U.S. DEPARTMENT OF COMMERCE PATENT OFFICE Washington, D.C. 20231 UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,404,136October 1, 1968 William A. P. Black et a1.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 7, line 35, "C H N 0 should read C H N O Column 9, line 14,"58.27" should read 58.37 line 50, "C H N O should read C H N O Column10, line 21,

Signed and sealed this 17th day of February 1970.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Edward M. Fletcher, Jr.

Commissioner of Patents Attesting Officer

2. POLY(1,2:5,6 - DI - O-ISOPROPYLIDENE-3-O-VINYL-A-DGLUCOFURANOSE).